The production of biodiesel through transesterification routes generates large amounts of glycerol, approximately 10 m3 for every 90 m3 of the biodiesel produced. Taking into account this scenario, the valorization of glycerol using chemical routes that could be operated in biodiesel industry constitutes a promising approach to achieve added-value products. An interesting option is the production of ethers, which can be used as fuel additives in diesel engines to improve the combustion efficiency, reducing soot emission and increasing cetane index. In this study, a purification route was applied to crude glycerol and its valorization by etherification was evaluated. The glycerol contents of purified samples were above 98% wt. The purified and commercial glycerol was used to obtain ethers. Etherification reactions were carried out with different alcohols (ethanol, isopropanol and 3-methyl-1-butanol) into a batch reactor, using small amount of Amberlyst 15 as a catalyst, at autogenous pressure and solvent-free conditions. The glycerol conversion, selectivity and yield to ethers were evaluated. A glycerol conversion of 97% wt. with selectivity of 80% to monoether was obtained when using ethanol. For isopropanol, the glycerol conversion was up to 95% (76% of monoether and 22% of diether). However, the selectivity to ethers for 3-methyl-1-butanol was negligible (<3% wt.). A process simulation for purification and etherification steps integrated with a biodiesel production was assessed in terms of productivity and energy consumption, considering different scenarios of glycerol/alcohol molar ratios.